Strange development/storage problem

I was looking through some loose negatives that for whatever reason I hadn't filed and probably not even more than glanced at, and came upon one that had some variable overal yellow/orange stains and then other strange defects on it. If I had to guess, it's a combination of an oxidation/storage process and a development failure (including issues with very expired film). Below is an enlarged bit, photographed with a macro lens.

Film: TMAX 400, unknown age (possibly/probably expired a decade+)
Developer: Diafine (TMY works fine in Diafine in my experience), usually 3 min/4 min, film has good to high D max
Fixer: Ilford Rapid, probably 3 min
Wash: Ilford dump then generally some extra standing -- this film is zero-pink so it seems like it must have been pretty thoroughly washed
Drying: a few drops of surfactant in final rinse then hang to dry
Storage conditions: Loose in a container, open to air, subdued indoor light/no direct sunlight, dewpoint 35-60F generally "fairly dry," about 2 yr

I put this through 2-3 min of fixer again, then a wash, and the orange tint is mostly gone. However the splotchiness mostly remains.

It's possible I did something out of my ordinary process, but given that this is TMY and has no pink left in it, I doubt that failure to wash thoroughly was part of that. I've developed a couple hundred or so rolls of film in Diafine so it's unlikely I completely left the rails there, and the overall exposure/development is spot on.

But the overall "orange" varies across the film like it wasn't washed thoroughly. The defects, as you can see, vary both according to location and underlying exposure, which I also find strange. Normally I think "orange/amber = oxidation" but I just don't know what that could be.

I don't seem to have scanned or photographed these negatives around the time that I developed them so I can't say what they looked like at the time.

It's also possible that I developed them in a Darkroom Cookbook "version" of Diafine, which I was using around that time with complete success when Diafine was not available. (I now have a new quart pack made, another dry quart pack and a gallon pack. I'm good.)

Maybe a process problem, maybe just a weird combination of things.

I shoot mostly expired film and I just go with whatever shows up (if I want nice clean photos, I have digital gear). I haven't seen anything like this before. Thoughts?

This is simply plain old silvering out due to insufficient fixing. You mention 3 minutes in rapid fixer, which for a T-grain emulsion is way too brief, generally. The improvement due to re-fixing supports this. The fact that it doesn't entirely go away is probably due to enough silver having had the opportunity to turn to a metallic state, which makes it equivalent to the actual image. I.e. there's nothing you could do about it that wouldn't also affect the image itself.

I've got some RC prints that show the same effect; it's pretty neat, actually, especially because it gives this bronzing effect that adds a nice sheen to it. But it's of course a bit of a concern in terms of archival stability (quod non!)

Cherish the cool effect. There's not much else you can do at this point.

koraks said:

This is simply plain old silvering out due to insufficient fixing. You mention 3 minutes in rapid fixer, which for a T-grain emulsion is way too brief, generally. The improvement due to re-fixing supports this. The fact that it doesn't entirely go away is probably due to enough silver having had the opportunity to turn to a metallic state, which makes it equivalent to the actual image. I.e. there's nothing you could do about it that wouldn't also affect the image itself.

I've got some RC prints that show the same effect; it's pretty neat, actually, especially because it gives this bronzing effect that adds a nice sheen to it. But it's of course a bit of a concern in terms of archival stability (quod non!)

Cherish the cool effect. There's not much else you can do at this point.

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I don't see how insufficient fix time or depleted fixer could create an effect like this. I always check visually that my negatives are properly fixed. There is not a hint of haze on this negative.

In general, fresh fixer with agitation will completely clear whatever negatives you put in it in considerably under a minute. Sometimes seconds. I judge fixer depleted when I pop the lid at 1 minute and the negatives aren't completely free of haze.

Long fix times with TMAX are related to that stupid dye.

Small traces of remaining silver halide can be difficult to spot on an emulsion. Heavy deposits will be easy to see as milky clouds or areas, but slight remnants will fall away against the somewhat matte appearance of the emulsion itself. Yet, such a thin layer can create quite a bit of optical density as it silvers out.

Furthermore, I think you're underestimating the influence of silver halide crystal shape on fixing. Tabular grain films really do fix much slower since the grains aren't really clumps, but thin plaques, a bit like roofing tiles at a micro scale. The flat surfaces of these grains are difficult for the fixer to attack, so that fixing action only occurs at the edges. This results in far slower fixing speeds.

J N said:

Long fix times with TMAX are related to that stupid dye.

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That's a different issue.

You don't have to take my word for it, but I really think that the problem you're showing here relates to insufficient fixing. Everything you've said and shown so far points in this direction.

If you want an alternative explanation because you don't like any of the above, might be simple mould. A treatment with a weak solution of peroxide or even chlorine bleach helps to kill the growth (emphasis on WEAK solution as a strong solution will damage the emulsion). However, damage to the emulsion due to organisms eating away at it will be irreversible.

Better photographs of the emulsion surface may help in proving what problem(s) your negatives have. A combination is of course also possible.

Here, does this look familiar to you:

koraks said:

Here, does this look familiar to you:
View attachment 354371

View attachment 354373
View attachment 354374
View attachment 354375

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This should rather be from not washing enough... I have quite a few 20 year old prints, some are quite yellowed. I also have some where, due to insufficient fixation, the residual silver has crystallized in the form of a metallic foil on the image

lamerko said:

I also have some where, due to insufficient fixation, the residual silver has crystallized in the form of a metallic foil on the image

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The crystallization/silvering out in an actual reflective silver layer is also visible in the first image I posted, as well as in virtually each sample out of that particular set.

There's no silvering out or bronzing. I've seen a few pounds of prints and negatives at antique fairs, some of which might have been useful as mirrors.

At the gross level the film looks like it has a variable thin coating of brown/orange material that suggests discoloration but not other damage. This discoloration was somewhat removed by a few minutes of fixer and a wash.

However at the grain level there are these apparently related defects. I don't think re-fixing had any effect on the defects, just their color.

"Does this look familiar to you?" -- Not in this case.

I think the film was old and damaged. If could have been exposed to temperatures from minus 60F to 100F several times, unexposed. Literally. It was stored in a cabin in central Alaska for a few years, along with a bunch of other film that seems to have survived mostly fine. So I can understand defects at the grain level but what's with the orange?

I've been thinking that the discoloration developed in the past couple years of storage, but it's possible the film looked like that shortly after development. I didn't know. I probably developed a half dozen rolls of color and b+w after that shoot but apparently I only ever scanned a roll of cross processed color and just chucked the rest into a bin for later.

I spent a few minutes just now seeing if I could take another useful photo or two but I couldn't find a "pose" that was on point. Will try again later after I've gained weight.

Alright, thanks for clarifying. In case you manage to get some better photos, I'm sure this could prove very useful. I remain with my second suggestion of mould or maybe fungal growth. Yellows and oranges are pretty common hues could match with this quite well.

Maybe the refixing made a difference due to the sulfite in the fixer bleaching out the organic dyes of the biological growth and the fixing itself didn't actually do much at all. If you have any sulfite or hypo clear, see if that achieves the same.

while only common on Microfilm, thet may be related to "redox Blemishes" that can be brought on by the packaging the developed film is stored in.

https://www.filmcare.org/vd_redoxblemishes.php will get you started. web searches for "redox Blemishes" will give you more links...

I recall one situation where we had 500 rolls of Microfilm that had been wound by the lab on Generic Plastic reels and stored in Cardboard boxes. the reels were getting brittle and over half of the rolls had spots. we were told to rewind the film onto Kodak White return reels, and rehouse the film in Kodak plastic boxes, labeled with special plastic labels The Kodak boxes had to be new, and not ones that had previously had a label on them. fortunatly there were seneral sites with the same problem and so they were able to get the boxes and reels in a bulk shipment and parcel it out to the various sites.

@cmacd123 thanks for posting that; I never heard of this, but it makes perfect sense and it seems to at least partly fit the defects on my prints as well!

It would also be a mechanism that is unrelated to fixing, which agrees with @J N's expectations.